CN105753633B - Slow down the method for by-product formation in alkyl halide compound production process - Google Patents
Slow down the method for by-product formation in alkyl halide compound production process Download PDFInfo
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- CN105753633B CN105753633B CN201610131863.1A CN201610131863A CN105753633B CN 105753633 B CN105753633 B CN 105753633B CN 201610131863 A CN201610131863 A CN 201610131863A CN 105753633 B CN105753633 B CN 105753633B
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000006227 byproduct Substances 0.000 title claims abstract description 27
- -1 alkyl halide compound Chemical class 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 title abstract description 11
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 50
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 32
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical group CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 9
- 239000003426 co-catalyst Substances 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 3
- PNLQPWWBHXMFCA-UHFFFAOYSA-N 2-chloroprop-1-ene Chemical compound CC(Cl)=C PNLQPWWBHXMFCA-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 238000007701 flash-distillation Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 5
- GZETWZZNDACBTQ-UHFFFAOYSA-N [Cl].C=C Chemical group [Cl].C=C GZETWZZNDACBTQ-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 abstract description 24
- 238000011084 recovery Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 10
- RWNKSTSCBHKHTB-UHFFFAOYSA-N Hexachloro-1,3-butadiene Chemical compound ClC(Cl)=C(Cl)C(Cl)=C(Cl)Cl RWNKSTSCBHKHTB-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 229950011008 tetrachloroethylene Drugs 0.000 description 5
- ZBZJXHCVGLJWFG-UHFFFAOYSA-N trichloromethyl(.) Chemical compound Cl[C](Cl)Cl ZBZJXHCVGLJWFG-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 210000003298 dental enamel Anatomy 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- VVWFZKBKXPXGBH-UHFFFAOYSA-N 1,1,1,3,3-pentachloropropane Chemical compound ClC(Cl)CC(Cl)(Cl)Cl VVWFZKBKXPXGBH-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical compound C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate tribasic Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0257—Phosphorus acids or phosphorus acid esters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0257—Phosphorus acids or phosphorus acid esters
- B01J31/0258—Phosphoric acid mono-, di- or triesters ((RO)(R'O)2P=O), i.e. R= C, R'= C, H
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/275—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of hydrocarbons and halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to the methods for slowing down by-product formation in alkyl halide compound production process, specifically disclose the method for producing alkyl halide compound, more specifically, for producing compound 1,1,1,3, the improved method of 3- pentachloropropane (HCC-240fa), slows down derived from vinyl chloride (CH2=CHCl) by-product formation.The present invention can also be used to produce other alkyl halide compounds, such as HCC-250 and HCC-360.Embodiments of the present invention include 1,3,3,5, the 5- chlordene pentane and 1 for slowing down 1 in HCC-240fa production process, the method for the formation of 1,1,3,5,5- chlordene pentane, wherein startup stage be over and operate continuously have begun after just by FeCl3It is introduced into reactor.In a preferred embodiment, " pre- chelating " FeCl that will be concentrated in catalyst recovery tower after continuous operation has begun3It is introduced into reactor.
Description
The application is the divisional application of an application for a patent for invention, and the applying date of female case is on May 30th, 2012, application
Number for 201280026942.6 (PCT/US2012/039922), entitled " subtract in alkyl halide compound production process
The method that slow by-product is formed ".
Cross reference to related applications
This application claims co-owning of submitting on June 3rd, 2011 and the U.S. Provisional Patent Application sequences of co-pending
Number 61/492931 domestic priority, the disclosure of which is incorporated herein by reference.
What the application also required to submit on June 3rd, 2011 co-own and the U.S. Provisional Patent Application of co-pending
The domestic priority of serial number 61/492898, the disclosure of which is incorporated herein by reference.
Technical field
The present invention relates to the method for producing alkyl halide compound, more specifically to for producing 1,1,1,3,
The improved method of 3- pentachloropropane (HCC-240fa).The present invention is also used to produce other alkyl halide compounds, such as HCC-250 and
HCC-360。
Background technique
Compound 1,1,1,3,3- pentachloropropane (HCC-240fa) is for producing 1,1,1,3,3- pentafluoropropane (HFC-
Raw material 245fa), HFC-245fa are the chemicals for not destroying ozone layer, and can be used as foaming agent, energy transmission medium etc.
Deng.The addition reaction for being used to prepare useful halogenated alkane (such as HCC-240fa) is well known in the art.For example, the U.S.
Patent 6313360 teach the method for production HCC-240fa, are contained by existing in catalyst mixture and being enough to generate
Make carbon tetrachloride (CCl under conditions of the product mixtures of HCC-240fa4) catalysis to carry out is reacted with vinyl chloride (VCM)
Agent composition includes organophosphorus ester, such as tributyl phosphate (TBP), metallic iron and iron chloride.Then, by by its with react
Object, catalyst and by-product separation are to recycle the 240fa product.Referring also to United States Patent (USP) 5902914,6187978,
6500995,6552238,6720466, No. 7112709 and U.S. Patent Publication 2008/0091053.All these references
The disclosure of document is incorporated herein by reference.
Applicants have unexpectedly found that when using catalyst mixture disclosed in United States Patent (USP) 6313360, i.e. TBP, gold
When belonging to iron and iron chloride, in CCl4In the reaction process of VCM, especially in the start-up course of reaction, a large amount of CCl are generated4
Derivative (originating) by-product, such as carbon trichloride, tetrachloro-ethylene, chloroform and hexachlorobutadiene.The shape of these by-products
At the significant decrease for leading to HCC-240fa selectivity.
Therefore, present inventors have recognized that needing the improved starting method for producing HCC-240fa.Reality of the invention
The mode of applying solves this problem.
Applicant further found that after above-mentioned initial start, for example, the reaction as intermittently operated or preferably as
When continuous operation carries out, the HCC-240fa finally measured comprising concentration (concentrated) in reactor, such as with possible big
The composition of the 60wt% of Organic Content in the reactor.In these cases, when by iron powder (Fe0) and tributyl phosphate
(TBP) when the fresh catalyst formed is introduced into reactor, VCM is preferentially reacted with HCC-240fa rather than CCl4, and then shape
At undesirable by-product, such as 1,1,3,3,5,5- chlordene pentane (main) and 1,1,1,3,5,5- chlordene pentane (secondary).For
For the sake of convenient, these chlordene pentanes are known as by-product derived from vinyl chloride.Depending on TBP concentration, 1,1,3,3,5,5- chlordene
The selectivity of pentane can reach 65%, this leads to the significant yield losses of required HCC-240fa product.
Therefore, present inventors have recognized that needing that by-product derived from these vinyl chloride can be avoided the formation of during the process
The means of object.Embodiments of the present invention additionally provide a solution to this problem.
Summary of the invention
Therefore, the present invention relates to the improved methods of production alkyl halide compound, and relate more specifically to production 1, and 1,1,
The improved method of 3,3- pentachloropropane (HCC-240fa) compound.The present invention can also be used in the production of other alkyl halide compounds
Process, such as HCC-250 and HCC-360.
It in some embodiments, is usually opening for intermittent reaction including transformation to the improvement of HCC-240fa production method
Dynamic reaction, wherein being reduced by catalyst choice appropriate from CCl4By-product.Specifically, it has been found that reacting
Startup stage during, FeCl3It should be minimized or be omitted completely.
It in some embodiments, include the reaction (post being transformed after starting to the improvement of HCC-240fa production method
Start-up reaction), i.e., HCC-240fa has begun to be formed, and reaches level of reactivity or Gao Shui in the reactor
After flat.The high level of the HCC-240fa in reactor Organic Content can be different, but is usually at least about
35% or 45% or 55% or 65% or higher.In these high levels, HCC-240fa can be reacted with VCM, rather than with
CCl4, cause the loss of undesirable by-product and required product.This stage of reaction that can intermittently or serially carry out, including it is logical
Another catalyst choice appropriate is crossed to reduce the generation of by-product.Specifically, in this section in reaction, by FeCl3With
It is very suitable as catalyst, because it inhibits the formation of by-product derived from undesirable vinyl chloride.
In one embodiment, the present invention relates to the improved methods of production HCC-240fa.This aspect of the invention can one
As property be described as formation for slowing down by-product derived from vinyl chloride in HCC-240fa production process, especially 1,1,
The method of the formation of 3,3,5,5- chlordene pentanes, wherein only after interval startup stage has carried out, and preferably upon it is continuous
After operation has begun, by FeCl3It is introduced into reactor.
Work as FeCl3When being added to reactor, it is in situ with the tributyl phosphate being present in reactor (or with it is other organic phosphorus
Acid esters) chelating.If pure or untreated FeCl3It chelates in the reactor, then the FeCl3Referred to herein as chelate
FeCl3.Another kind is by FeCl3The mode being added in reactor is the pre- chelating being concentrated include in reactor effluent stream
FeCl3, and be recirculated in reactor.Pre- chelating FeCl3It is herein defined as preferred catalyst.
Applicants have discovered unexpectedly that in the presence of iron chloride (chelating or in advance chelate), it is undesirable to by-product 1,1,
The formation of 3,3,5,5- chlordene pentane is substantially suppressed to about 5% or lower.Therefore, in the present invention, raw in formerly reacting
At FeCl3Or preferred " pre- chelating " FeCl3It is introduced into processing (processing) reactor, to prevent or reduce not
The formation of by-product derived from desired vinyl chloride, that is, 1,1,3,3,5,5- chlordene pentane and 1,1,1,3,5,5- chlordene pentane.
The present invention can also be used in the production process of other alkyl halide compounds, such as HCC-250 and HCC-360:
(1) HCC-250 can be by CCl4It is made with ethylene according to following reaction:
CCl4+ CH2 = CH2 → CCl3CH2CH2Cl
In this case, it is by the undesirable by-product that treatment conditions teaching herein reduce or eliminate
CCl3CH2CH2CH2CH2Cl and ClCH2CH2CCl2CH2CH2Cl。
(2) HCC-360 can be by CCl4It is made with 2- chloropropene according to following reaction:
CCl4+ CH2 = CClCH3 → CCl3CH2CCl2CH3
In this case, it is by the undesirable by-product that treatment conditions teaching herein reduce or eliminate
CCl3CH2CCl(CH2CCl2CH3)CH3And CH3CCl2CH2CCl2CH2CCl2CH3。
The personnel of ordinary skill with one or more fields according to the present invention should be appreciated that herein for this hair
Any feature described in bright any particular aspects and/or embodiment, can be with any of the invention its described herein
Any other feature of one or more of its aspect and/or embodiment combines, if can suitably be transformed to ensure group
The compatibility of conjunction.Such combination is considered as a part of the invention desired by the disclosure.
It should be understood that foregoing general description and following detailed description are all only exemplary and explanatory,
Rather than the limitation to claimed invention.Based on the thinking to specification and invention disclosed herein practice, Qi Tashi
The mode of applying will be apparent to those skilled in the art.
Specific embodiment
Starting reaction
In some embodiments, which carries out in the glass lined reaction vessel equipped with blender.Of the invention
In embodiment, using only as the Fe of catalyst0Iron powder and organophosphorus compounds (such as tricresyl phosphate as co-catalyst
Butyl ester (TBP)) Lai Qidong vinyl chloride reacts with carbon tetrachloride to form HCC-240fa, the use of iron chloride is omitted.
Iron powder for use in the present invention is preferably the fine powder of pure metal iron, and preferred granularity is less than 325 mesh.Iron powder can pass through
Any mode is added in reactor, but the powder slurries being located in carbon tetrachloride, tributyl phosphate or both mixture are excellent
Choosing.Although iron powder is preferably, any irony article (iron object), such as iron ball, iron wire, iron filings to can be used.
Co-catalyst TBP is chelating agent, and can also act as assist in solvation solid catalyst.Iron powder and tricresyl phosphate fourth
The molar ratio of ester can be about 0.05:1 to about 500.0:1, and preferably from about 1.0:1 to about 100.0:1, even more preferably about 1.5:1 is extremely
About 10:1.Catalyst preferred concentration in the reactive mixture is about 0.001~about 20wt%, preferably from about 0.01~about 10
Wt%, even more preferably about 0.1~about 5 wt%.Under normal circumstances, CCl4Molar ratio with VCM is about 0.02:1 to about 50:1.
Preferably, which is about 0.1:1 to about 4.0:1, even more preferably about 1:1 to about 3:1.
Available other organophosphorus ester co-catalysts herein are as follows: triphenyl phosphate, tributyl phosphate, tripotassium phosphate
Ester, triethyl phosphate, tricresyl phosphate propyl ester or any similar organophosphorus compounds and two or more these it is mixed
Close object.
In interval start-up course, first by a certain amount of CCl4Loading is pre-purged anti-(with inert gas such as nitrogen)
It answers in device, followed by iron powder, tributyl phosphate and CCl4Slurry mix.Then, reactor is heated to about 40 under stirring
DEG C~about 180 DEG C of temperature, preferably from about 85 DEG C~about 150 DEG C.Then it is fed into VCM as steam in reactor until quilt
The vinyl chloride of carbon tetrachloride interval consumption in reactor is equivalent to target molar ratio.
In the preferred embodiment, the initial charge of vinyl chloride is introduced without the use of flow control mechanism (for example, RCV, needle
Type valve etc.), it is therefore an objective to keep initial feed rate maximum.Reaction temperature and catalyst activity inherently determine reactor pressure,
It is preferably the psia of 30 psia~60.It is preferred that carrying out intermittent reaction, 95% VCM conversion ratio is higher than until realizing.At certain
In a little embodiments, the operation is then transited into continuous operation mode.
Continuous operation
In continuous operation, in a ratio of the desired by CCl4It is continuously fed into reactor with VCM.In method of the invention
In, FeCl3, iron powder and TBP can periodically or continuously be added in reactor, but preferably continuous mode.Any shape can be used
The FeCl of formula3.Non-limiting example includes solid FeCl3、FeCl3Solution and FeCl3Suspension.It can be used to prepare FeCl3Solution
Or the non-limiting example of the solvent of suspension includes CCl4, TBP, HCC-240fa and chlordene pentane isomers.
The residence time that the reaction preferably carries out is about 0.01h~about for 24 hours, preferably from about 1h~about 12h.Reaction condition choosing
It is selected as realizing the generation of high VCM efficiency, high HCC-240fa yield and low by-product.Table 1 lists selected reaction condition.
Table 1
In continuous operation, reactor content is constantly extracted out by the pipe immersed in liquid.Passing through retention abrasive grit
After the filter of son, it includes unreacted CCl that reactor effluent stream, which is flashed to remove,4It is if any with VCM() charging with
And " top " stream of HCC-240 reaction product, and retain catalyst/co-catalyst mixture.The distillation can at one or
It is executed in multiple destilling towers, the destilling tower is well known in the art.
Preferably, it is described flash distillation with two steps progress: first, flash lower than reaction temperature temperature and certain pressure under into
Row, preferably carries out, under vacuum to remove any unreacted CCl4And/or VCM, it is another followed by low pressures
Vacuum flashing, to remove HCC-240fa reaction product." bottom " stream includes iron chloride, tributyl phosphate, HCC-240, chlordene
Pentane isomers and possible other high boiling components.
In a preferred embodiment of the invention, including in advance FeCl is chelated3" bottom " stream be recirculated back to reactor
In.With with the pure or fresh FeCl that introduces as described above3Identical mode, including the pre- chelating FeCl in the stream3It plays
The effect for inhibiting 1,1,3,3,5,5- chlordene pentane to be formed.
Through CCl distill, unreacted4In recyclable time reactor of VCM.It can be using periodically removing to avoid heavy
The accumulation of by-product such as chlordene pentane isomers in catalyst recycle stream.
In the subsequent step of the method, the present invention provides by distilling come purification of crude product.Vacuum topping is about 5
~about 200mm mercury column and about 50 DEG C~about 150 DEG C of temperature carry out, with recovery product.It has been found that being esterified when in organic phosphoric acid
Close object, when as carried out the purification step in the presence of tributyl phosphate or other metal-chelating compounds, the distillation of purified product
Yield significantly improves.
While not wishing to the constraint by any specific theory, but it is believed that tributyl phosphate, which plays, prevents HCC-240fa
The effect that product decomposes.Therefore, in a preferred embodiment, purification step includes adding a certain amount of to be enough to improve HCC-
The metal-chelating compound of 240fa product yield,.Preferably, using the tributyl phosphate of 5wt%.
If necessary, iron catalyst used in the alkyl halide compound production of this paper can be separated by using electromagnetism
Device (EMSU) is captured and is recycled.When energization, the EMSU plays the role of removing iron particle from reactor effluent；
When power-off, can recoil to return in reactor by the iron particle that EMSU is captured is used further to required alkyl halide compound such as HCC-240fa
Continue produce.
Following non-limiting embodiment is used to further illustrate the present invention.
Embodiment 1
The batch mixed in 5 gallons of enamel jacketed reactors being purged through nitrogen, containing 15.1 lbs carbon tetrachloride
241g iron powder, 70g iron chloride and 346g tributyl phosphate.During preheating, using low-pressure steam, 90 DEG C are brought the mixture to
Not condensate is discharged in temperature.In the temperature, 4.1 lbs vinyl chloride are introduced into reactor, and made one section of its consumption about 1 day
Time.Sample is recycled from reactor at the end of reaction, and is analyzed with gas-chromatography.Gas-chromatography the result shows that,
Reactor to HCC-240fa is selectively 76%.Tetrachloro including carbon trichloride, tetrachloro-ethylene, chloroform and hexachlorobutadiene
Change carbon by-product total accounts for total reactor selectivity 12%.
Embodiment 2
In rated pressure (pressure rated) test tube of 150cc, by 2.53g tributyl phosphate, 0.51g tri-chlorination
Iron and 1.8g iron powder are mixed with 50g carbon tetrachloride.The container is immersed in the hot oil bath for being heated to 90 DEG C.The chemical reagent exists
It continuously stirs at this temperature 4 hours.After the incorporation time past, test tube is taken out from oil bath, and be cooled back to room temperature.It samples and is used in combination
GC analysis.GC is analysis shows there are by-product derived from carbon tetrachloride, including carbon trichloride, tetrachloro-ethylene, chloroform and six
Chlorobutadiene.The reaction carries out in the presence of no vinyl chloride.
Embodiment 3
It is similar to Example 2, in the rated pressure test tube of 150cc, by 2.53g tributyl phosphate and 1.8g iron powder with
The mixing of 50g carbon tetrachloride, is omitted the addition of iron chloride.Similarly, container is immersed in the hot oil bath for be heated to 90 DEG C and is held
It is 4 hours continuous.Mixture is cooled to room temperature, and recycles sample and is analyzed for GC.Data are displayed without the sign of reaction because not having
There is by-product to be formed.
Embodiment 4
The addition of ferric trichloride is omitted, by 136g phosphoric acid in the 5 gallons of enamel jacketed reactors purged through nitrogen
Tributyl and 300g iron powder (325 mesh) are added in 41 lbs carbon tetrachloride.During preheating, using low-pressure steam, make to mix
Object reaches 100 DEG C of temperature, and not condensate is discharged.In the temperature, vinyl chloride steam is injected into liquid using reactor dip pipe
In mixture.During adding vinyl chloride, make feed flow without using external control (control valve).
Carry out reaction until 8.3 lbs vinyl chloride are added into reactor.After reaction, recycles sample and analyzed with GC.
The result shows that be selectively 90.7% to the total reactor of HCC-240fa, wherein comprising carbon trichloride, tetrachloro-ethylene, chloroform and
The by-product of hexachlorobutadiene, which amounts to, constitutes 4.9%.
Embodiment 5
The way similar with condition disclosed in embodiment 3 is followed, in the 5 gallons of enamel jacketed reactions purged through nitrogen
136g tributyl phosphate and 300g iron powder (325 mesh) are added in 41 lbs carbon tetrachloride in device, equally omission iron chloride.Together
Reactor is heated to 100 DEG C in warm and is vented by sample.However, in the temperature, using pneumatic research control valve with by
Vinyl chloride steam is introduced into the liquid mixture in reactor by the rate of control.
Carry out reaction until 8.3 lbs vinyl chloride are added into reactor.After reaction, recycles sample and analyzed with GC.
The result shows that be selectively reduced to 85.3% to the total reactor of HCC-240fa, wherein carbon trichloride, tetrachloro-ethylene, chloroform and
Hexachlorobutadiene, which amounts to, constitutes 10.8%.
Embodiment 6
In the rated pressure test tube reactor of 150cc, by the 1 of 24.5g, 1,1,3,3- pentachloropropane, tetra- chlorination of 10.5g
Carbon, 0.35g tributyl phosphate and 1.23g iron powder (325 mesh) mixing, and purged with nitrogen.Test tube is immersed in hot oil bath and pre-
Heat is to 90 DEG C.Vinyl chloride steam is introduced into test tube reactor in the temperature.After adding vinyl chloride, the temperature of oil bath is risen to
100℃.Reaction was cooled down if past 5 hours, and the sample of withdrawal liquid medium is analyzed for GC.This analysis shows,
The selectivity of 1,1,3,3,5,5- chlordene pentane is 28.8%.The source cylinder (source cylinder) of vinyl chloride shows testing
Duration in introduce 13.5g material.
Embodiment 7
It is similar to Example 6, in the 150cc rated pressure test tube reactor purged through nitrogen, by 24.5g 1,1,1,
3,3- pentachloropropane, 10.5g carbon tetrachloride, 0.35 gram of tributyl phosphate, 0.07g iron chloride and 1.23g iron powder (325 mesh) are mixed
It closes.Equally test tube is immersed in hot oil bath and is preheated to 90 DEG C.In the temperature, vinyl chloride steam is introduced into test tube reactor
In, and temperature rises to 100 DEG C again.Reaction was cooled down if past 5 hours, and the sample of withdrawal liquid medium is for GC points
Analysis.This analysis shows, the selectivity of 1,1,3,3,5,5- chlordene pentane is 7.9%.5.6g chloroethene is introduced into reactor
Alkene.
Embodiment 8
The use of pure phosphoric acid tributyl and iron chloride shown in alternate embodiment 7, it is specified in the 150cc purged through nitrogen
In pressure tube reactor, the 1 of 24.5g, 1,1,3,3- pentachloropropane, 10.5g carbon tetrachloride, 1.08g are recycled from catalyst
Tower recycles and includes bottom product and 1.23g iron powder (325 mesh) mixing of 17wt% tributyl phosphate.Test tube is immersed into hot oil bath
In and be preheating to 90 DEG C.In the temperature, vinyl chloride steam is introduced into test tube reactor, and temperature rises to 100 DEG C again.?
Reaction was cooled down after past 5 hour, and the sample of withdrawal liquid medium is analyzed for GC.Should analysis shows, 1,1,3,3,5,5-
The selectivity of chlordene pentane is 3.1%.6.4g vinyl chloride is introduced into reactor.
As used herein, unless context clearly states otherwise, singular " a(mono-) ", " an(is a kind of) "
" the(is somebody's turn to do) " it include plural.In addition, equivalent, concentration or other values or parameter are with range, preferred scope or a system
The high preferred value and low preferred value of column are when providing, it is thus understood that specifically disclose by any range limit or high preferred value with it is any
All ranges that any pairing of range lower limit or low preferred value is formed, no matter whether the range is separately disclosed.Remember when herein
When having carried numberical range, unless otherwise indicated, the range be intended to include its endpoint and all integers within the scope of this and point
Number.When limiting range, it is not meant to limit the scope of the present invention to documented particular value.
It should be understood that above description is merely illustrative the present invention.This field without departing from the present invention
Technical staff can be designed various alternative solutions and modification.Therefore, the present invention is directed to cover to fall within the scope of the appended claims
All these alternative solutions, modification and variant.
Claims (9)
1. for the method by carbon tetrachloride and alkene production alkyl halide compound, wherein during making reaction startup stage
CCl4Derivative by-product is minimized, and the method includes by ferrous metal catalyst and as the one or more of co-catalyst
The step of organophosphorus compounds is reacted, wherein the method further includes following steps, wherein in this method
After startup stage has carried out and produced a certain amount of alkyl halide compound, by FeCl3It is introduced into reactor.
2. according to the method described in claim 1, wherein the alkene is selected from vinyl chloride, ethylene and 2- chloropropene.
3. according to the method described in claim 1, wherein the alkyl halide compound is selected from HCC-240fa, HCC-250 and HCC-
360。
4. according to the method described in claim 1, wherein the ferrous metal catalyst has selected from iron powder, iron ball, iron wire, iron filings
And the form of their mixture.
5. according to the method described in claim 1, wherein the organophosphorus ester co-catalyst is selected from tributyl phosphate, tricresyl phosphate
Methyl esters, triethyl phosphate, tricresyl phosphate propyl ester, triphenyl phosphate and two or more in them mixture.
6. according to the method described in claim 1, wherein the alkyl halide compound includes HCC-240fa, the olefinic compound
Object includes vinyl chloride, and the co-catalyst includes tributyl phosphate.
7. according to the method described in claim 6, it further includes following steps: ferrous metal is removed from catalyst mixture, with
Flash distillation HCC-240fa product stream from catalyst mixture afterwards to separate HCC-240fa, unreacted CCl4With unreacted chlorine
Ethylene, and remaining catalytic component is recycled to the reactor.
8. according to the method described in claim 7, wherein the ferrous metal catalyst includes the fine powder of pure metal iron.
9. according to the method described in claim 8, wherein the ferrous metal catalyst passes through the powder slurry in carbon tetrachloride
Expect or by the powder slurries in tributyl phosphate or by being located at CCl4With the powder slurry in tributyl phosphate mixture
Material is added in reactor.
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| US201161492898P | 2011-06-03 | 2011-06-03 | |
| US201161492931P | 2011-06-03 | 2011-06-03 | |
| US61/492898 | 2011-06-03 | ||
| US61/492931 | 2011-06-03 | ||
| US13/481,121 US8835702B2 (en) | 2011-06-03 | 2012-05-25 | Method for mitigating the formation of by-products during the production of haloalkane compounds |
| US13/481121 | 2012-05-25 | ||
| CN201280026942.6A CN103562165B (en) | 2011-06-03 | 2012-05-30 | The method that by product is formed is slowed down in alkyl halide compound production process |
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| US (1) | US8835702B2 (en) |
| EP (1) | EP2718250A4 (en) |
| JP (2) | JP6072780B2 (en) |
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| US9289758B2 (en) | 2013-01-22 | 2016-03-22 | Axiall Ohio, Inc. | Processes for producing chlorinated hydrocarbons and methods for recovering polyvalent antimony catalysts therefrom |
| US8889930B2 (en) | 2013-01-22 | 2014-11-18 | Axiall Ohio, Inc. | Process for producing chlorinated hydrocarbons |
| US8859829B2 (en) * | 2013-03-14 | 2014-10-14 | Honeywell International Inc. | Stabilizer and inhibitor for chloropropenes, such as tetrachloropropene 1,1,2,3-tetrachloropropene (1230xa), used in the manufacture of 2,3,3,3-tetrafluoropropene (1234yf) |
| CN104230648A (en) * | 2013-06-18 | 2014-12-24 | 徐家乐 | Preparation method for synthesizing 1,1,1,3,3-pentachloropropane by carbon tetrachloride |
| US9139497B2 (en) | 2013-10-23 | 2015-09-22 | Axiall Ohio, Inc. | Process for producing chlorinated hydrocarbons in the presence of a polyvalent bismuth compound |
| CN104496745B (en) * | 2014-11-28 | 2018-05-04 | 巨化集团技术中心 | A kind of preparation method for synthesizing chlorohydrocarbon |
| CN104844413A (en) * | 2015-04-16 | 2015-08-19 | 宁波巨化化工科技有限公司 | Hexachlorobutadiene production process capable of achieving byproduct separation and raw material recovery |
| CN105622330A (en) * | 2016-01-26 | 2016-06-01 | 巨化集团技术中心 | Continuous preparation method of chlorohydrocarbons |
| CA3203916C (en) * | 2016-07-26 | 2024-01-23 | Occidental Chemcial Corporation | Methods for producing halogenated propanes |
| CN106380370B (en) * | 2016-08-17 | 2018-12-28 | 山东东岳化工有限公司 | A kind of short-cut method of chlorofluorocarbons resource utilization |
| JP7187573B2 (en) * | 2018-04-03 | 2022-12-12 | ブルー キューブ アイピー エルエルシー | Method for recycling catalyst in the production of chlorinated alkanes |
| WO2019195247A1 (en) * | 2018-04-03 | 2019-10-10 | Blue Cube Ip Llc | Improved processes for preparing halogenated alkanes |
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Also Published As
| Publication number | Publication date |
|---|---|
| RU2644560C2 (en) | 2018-02-13 |
| KR20140034894A (en) | 2014-03-20 |
| CN103562165A (en) | 2014-02-05 |
| US8835702B2 (en) | 2014-09-16 |
| JP2014524895A (en) | 2014-09-25 |
| CN103562165B (en) | 2016-03-02 |
| EP2718250A4 (en) | 2015-03-04 |
| JP6333939B2 (en) | 2018-05-30 |
| EP2718250A2 (en) | 2014-04-16 |
| CN105753633A (en) | 2016-07-13 |
| JP6072780B2 (en) | 2017-02-01 |
| US20120310021A1 (en) | 2012-12-06 |
| WO2012166759A2 (en) | 2012-12-06 |
| JP2017095470A (en) | 2017-06-01 |
| RU2013156264A (en) | 2015-07-20 |
| CA2836075A1 (en) | 2012-12-06 |
| WO2012166759A3 (en) | 2013-03-07 |
| MX2013013386A (en) | 2013-12-10 |
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